WO2005089549A1 - Use of epoxides as fungicides - Google Patents

Use of epoxides as fungicides Download PDF

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WO2005089549A1
WO2005089549A1 PCT/FI2005/050103 FI2005050103W WO2005089549A1 WO 2005089549 A1 WO2005089549 A1 WO 2005089549A1 FI 2005050103 W FI2005050103 W FI 2005050103W WO 2005089549 A1 WO2005089549 A1 WO 2005089549A1
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group
epoxide
ester
hydrocarbon
groups
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PCT/FI2005/050103
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English (en)
French (fr)
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Janne Hulkko
Salme Koskimies
Kari Rissanen
Marian Marttina
Reetta KYLÄKOSKI
Mia LÖIJA
Leena Paajanen
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Valtion Teknillinen Tutkimuskeskus
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Priority to EP05731351A priority Critical patent/EP1727425A1/en
Publication of WO2005089549A1 publication Critical patent/WO2005089549A1/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/20—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom three- or four-membered rings

Definitions

  • the present invention relates to reactive epoxides with polar groups, and to their use as mould preventive agents, and to a method for preventing mould build-up.
  • Publication WO 00/44836 discloses paint compositions wherein glycidyl ethers and glycidyl esters are used as coalescent agents.
  • EP 154806 describes ethers and esters of substituted epoxypropanols, having fun- gicidal effect.
  • JP 61155381 discloses brominated aromatic ethers of epoxypropanols useful as mould preventive agents.
  • fungicides are added to aqueous coating compositions for preventing mould growth.
  • the fungicides used are often compounds hazardous to health and environment.
  • Another object of the invention is the use of epoxides containing polar groups, preferably ether or ester groups, in coating compositions as agents for mould prevention.
  • polar groups preferably ether or ester groups
  • the object of the invention is the use of ethers and esters of epoxypro- panol that is of glycidyl ethers and glycidyl esters in coating compositions as agents for mould prevention.
  • an object of the invention is to provide a method for preventing formation of mould.
  • an ether or ester of an ethylenically unsaturated or saturated alcohol containing 2 - 20 carbon atoms with an ethylenically unsaturated alcohol or a carboxylic acid, all double bonds or at least part of the double bonds of said ether or ester being oxidized to give epoxy groups may be used as an agent for mould prevention/inhibition in aqueous or solvent-based coating compositions.
  • ethers and esters of epoxypropanol that is glycidyl ethers and glycidyl esters may be used as agents for mould prevention/inhibition according to the invention.
  • epoxides containing ether or ester groups preferably ethers and esters of epoxypropanol having mould preventive effect may be used according to the invention in aqueous coating compositions as agents for mould prevention/inhibition.
  • epoxide derivatives containing a large hydrocarbon residue particularly aliphatic and cycloaliphatic epoxide ethers and epoxide esters, provide also excellent coalescent properties, and further, that they may readily be dispersed in water and solvents, the solubility thereof in binder polymers present in the coating being good. This is due to particularly suitable molecular sizes, the presence of polar groups, and high boiling points of over 200 °C.
  • one or more ether(s) or ester(s) of an ethylenically unsaturated or saturated alcohol containing 2 - 20 carbon atoms with an ethyleni- cally unsaturated alcohol or a carboxylic acid, all double bonds or at least part of the double bonds of said ether or ester being oxidized to give epoxy groups, are used as coalescent agents in coating compositions based on water or solvents.
  • one or more epoxides selected from the group consisting of aliphatic epoxides, which may be linear aliphatic epoxide compounds, branched aliphatic epoxide compounds or cycloaliphatic epoxide compounds, with one or more epoxy groups, and glycidyl ethers and glycidyl esters having the epoxide in glycidyl position, and mixtures threof are used as agents for mould prevention in coating compositions.
  • aliphatic epoxides which may be linear aliphatic epoxide compounds, branched aliphatic epoxide compounds or cycloaliphatic epoxide compounds, with one or more epoxy groups, and glycidyl ethers and glycidyl esters having the epoxide in glycidyl position, and mixtures threof are used as agents for mould prevention in coating compositions.
  • the first group of the aliphatic epoxides consists of linear and branched aliphatic epoxides and the second group consists of cycloaliphatic epoxides.
  • the first group consists of aliphatic epoxide compounds that may be aliphatic ethers or esters.
  • aliphatic ethers the alcohol residue derived from a linear or branched monohydric alcohol, diol, triol, tetraol, or pentol with 2 - 20 carbon at- oms forms one or more ether group(s) with a linear or branched, saturated or ethylenically unsaturated alkyl halide.
  • alcohol residues of aliphatic esters derived from a linear or branched monohydric alcohol, diol, triol, tetraol, or pentol with 2 - 20 carbon atoms form one or more ester group(s) with a linear or branched, saturated or ethylenically unsaturated carboxylic acid.
  • the general Formula I below shows the structure of the aliphatic branhed and linear epoxide compounds.
  • R 1 and R 3 independently represent either hydrogen or a linear or branched, ethylenically unsaturated or saturated C ⁇ -C 16 hydrocarbon optionally having one or more ether group(s), further, one or both of R 1 and R 3 may contain one or more epoxy group(s), preferably R and R representing H or a Ci-C 8 hydrocarbon, particularly preferably R 1 and R 3 representing H or a -C o - hydrocarbon;
  • R 2 and R 4 independently represent either hydrogen or a linear or branched, ethylenically unsaturated or saturated C ⁇ -C 2 o hydrocarbon, or -(CH 2 ) n -COOR 5 or - (CH 2 ) m -OR , wherein the groups R and R independently represent a linear or branched, ethylenically unsaturated or saturated C 4 -C 16 hydrocarbon optionally having one or more epoxy group(s) or ester group(s), preferably the groups R 5 and R ⁇ representing C 4 -C ⁇ o hydrocarbons, particularly preferably the groups R 5 and R 6 representing C 4 -C 8 hydrocarbons, and further, R 2 and R 4 preferably represent H?
  • said aliphatic epoxide compounds may have from 1 to 6, preferably from 2 to 4 epoxy groups.
  • the epoxy groups originate from the oxy- dation of the double bonds present in alcohol and/or carboxylic acid residues of the ethers and esters.
  • Aliphatic ether and ester derivatives from di- and polyols may also be di-, tri-, tetra-, or pentaethers and -esters.
  • Carboxylic acid residues of the ester derivatives may be derived from linear or branched mono- or polybasic carboxylic acids with 2 - 20, preferably with 4 - 18 carbon atoms. Polybasic acids give mono-, di-, tri- etc. esters. Said esters may also comprise mixed esters.
  • the other group consists of cycloaliphatic epoxides.
  • the alcohol residue is derived from a linear or branched, mono- or polyhy- dric alcohol with 2 - 20 carbon atoms.
  • the alcohol residue may also be derived from an oligo- or polyether formed from two or more diols.
  • Carboxylic acid residues of cycloaliphatic epoxide esters are obtained from a Di- els-Alder reaction between a diene and a dienophile having a carboxylic group.
  • Cycloaliphatic epoxide esters may have from 1 to 4 epoxy groups obtained by oxydation of the double bonds in alcohol and/or carboxylic acid residues. Said esters may also have ether groups derived from a diene.
  • R 7 represents -O-, -CH 2 -, or -CH 2 CH 2 -;
  • R represents hydrogen, or a linear or branched, ethylenically unsaturated or saturated C 2 -C 2 o hydrocarbon that may have one or more epoxy group(s) and/or ether group(s), R 8 preferably representing a C 2 -C ⁇ o hydrocarbon, and particularly preferably R 8 representing a C 2 -C6 hydrocarbon.
  • R 9 represents either hydrogen or a methyl group
  • Exemplary aliphatic epoxide esters from monohydric alcohols include 2- methylpentyl-9,10-epoxydecanoate and 2-methyl-(oxiranyl)methyl-9,10- epoxydecanoate, whereas epoxide esters derived from dihydroxy alcohols are exemplified by 2-butyl-2-ethylpropyl-l,3-di(9,10-epoxyoctadecanoate), 2,2- dimethylpropyl-l,3-di(9,10-epoxydecanoate), and ethyleneglycol di(2,3- epoxypropanoate).
  • Cycloaliphatic epoxide esters include diethyleneglycol di(5,6-epoxy-2-norbornane carboxylate), and neopentylglycol di(5,6-epoxy-2-norbornane carboxylate).
  • Certain epoxide compounds which are ethers and esters of epoxypropanol, that is glycidyl ethers and glycidyl esters containing at least one epoxy group in the gly- cidyl position, known as coalescent agents, may be used as particularly effective mould inhibitors.
  • Preferable glycidyl ethers have structures of the general Formula III
  • R 10 represents a linear or branched, unsaturated or saturated C 2 -C 2 o hydrocarbon optionally having one or more hydroxyl group(s), preferably a C 4 -C ⁇ 8 hydrocar- bon, and X 1 represents hydrogen or a hydroxyl group.
  • the glycidyl ether may have from 1 to 5 glycidyl ether groups.
  • Preferable glycidyl esters have structures of the general Formula IN
  • R 11 represents a linear or branched, unsaturated or saturated C 2 -C 2 o hydrocarbon optionally having one or more hydroxyl group(s), preferably a C -C ⁇ 8 hydrocarbon, and
  • X 2 represents a methyl group, methylene hydroxy group, carboxyl group, or a lower carboxylate group.
  • Preferable lower carboxylate groups include methoxylate (-COOMe) and ethoxy- late (-COOEt).
  • Epoxide compounds with the epoxide in a non-glycidyl position are prepared by oxidizing a double bond.
  • Aliphatic epoxide ethers of the invention may be produced using the following synthesis comprising two steps, the first step comprising ether formation followed by epoxidation in the second step.
  • an alkyl halide is allowed to react with an alcohol.
  • Said etherification is carried out in a basic medium, preferably in the presence of potassium hydroxide.
  • toluene, DMSO, DMF, or THF may serve as the solvent of the organic phase.
  • Etherification is conveniently carried out at normal atmospheric pressure, and at temperatures ranging from 0 to 80 °C.
  • the reaction is preferably carried out at temperatures above 25 °C.
  • the product is recovered from the organic phase by extraction, filtration, and vacuum distillation.
  • the molar ratio of the alkyl halide to the hydroxyl groups of the alcohol reactant is from 1.0 to 1.1 fold.
  • an oxidation of the double bonds present in the ether to give epoxy groups may be achieved by reacting the ethylenically unsaturated ether with m-chloroperbenzoic acid, or with peracetic acid.
  • Preferable solvents include ethers and halogenated hydrocarbons.
  • a solution of peracetic acid in acetic acid, and perbenzoic acid may also used to selectively oxidize the double bonds.
  • Epoxydation is preferably carried out by reacting an ethylenically unsaturated ether with m-chloro-perbenzoic acid, dichloromethane serving as the solvent.
  • the reaction is allowed to proceed at 20 - 35 °C at least for 1 hour until the yield of the epoxide ether is at least 80 %, typically at least over 90 %.
  • the mo- lar ratio of the peracid to the double bonds of the ether reactant is from 1.1 to 1.3 fold.
  • the product is suitably recovered by washing the reaction mixture with sodium bisulfite solution, water, and a basic solution, and further by separating the organic layer and evaporating to dryness.
  • Terminal double bonds may be oxidized to give epoxy groups using aqueous hydrogen peroxide in a biphasic system, methyltrioxo rhenium serving as the catalyst and 3-cyanopyridine or pyrazole serving as the phase transfer agent of the catalyst.
  • Ethers, or chlorinated hydrocarbons, preferably dichloromethane, may be used as solvents.
  • the reaction is allowed to proceed for instance at 20 - 30 °C for at least 6 hours until the yield of the epoxide is at least 80 %, typically at least 85 %.
  • the molar ratio of hydrogen peroxide to the reacting double bonds of the ether is from 1.5 to 3.0 fold.
  • the amount of the catalyst used is preferably from 0.3 to 0.7 % by moles, the amount of 3-cyanopyridine being from 7 to 13 % by moles.
  • the reaction is terminated by adding ice and a catalytic amount of manganese dioxide to the reaction mixture.
  • the product may suitably be recov- ered from the mixture by extracting with organic solvents, preferably with dichloromethane, by concentrating to give an oil, by precipitating the 3- cyanopyridine N-oxide formed in the reaction with hexane, by filtration and evaporation to dryness.
  • Aliphatic epoxide esters of the invention may be produced using the following synthesis comprising two steps, the first step comprising esterification followed by epoxidation in the second step.
  • the reaction temperature for esterification varies typically from 110 to 190 °C, more suitably from 120 to 170 °C.
  • the reaction is carried out at normal atmospheric pressures.
  • about 0.1 - 10 % by moles of a catalyst may be used for the esterification.
  • Suitable esterification catalysts include p-toluene sulfonic acid, benzene sulfonic acid, sulfuric acid, tin and zinc salts or oxides, and titanates.
  • Suitable transesterification catalysts include alkali metal alkoxides such as potassium or sodium alkoxides, sulfuric acid, hydrochloric acid, and acidic ion exchange resins.
  • the esterification is carried out by reacting a saturated or ethylenically unsaturated carboxylic acid having a straight or bran- ched chain and having from 2 to 20 carbon atoms, with a saturated or ethylenically unsaturated mono- or polyhydric alcohol having a straight or branched chain and having from 2 to 20 carbon atoms.
  • Toluene or xylene may be used for removing water formed in the reaction.
  • Toluene or xylene serving as the solvent a typical temperature range during the reaction is about from 120 to 150 °C.
  • the reaction is allowed to proceed at least for 2 hours at said temperature, while water being formed in the reaction is removed to a separate intermediary device for wa- ter collection until the ester yield is at least 90 %, typically at least 97 %.
  • the molar ratio of the carboxylic acid to the hydroxyl groups of the alcohol reactant is from 1.0 to 1.1 fold.
  • p-toluene sulfonic acid is preferably used in an amount from 0.5 to 1.0 % by moles relative to the amount of the compound to be esterified.
  • the product is suitably recovered by washing the catalyst and the excessive acid from the reaction mixture with a basic solution, and then by separating the organic layer and evaporating to dryness.
  • the oxidation of the double bonds present in the ester to form epoxy groups may be carried out in an analogous way described above for the ethers.
  • Cycloaliphatic epoxide esters may be produced by reacting a diene such as cyclo- pentadiene or furane with a (meth)acrylate ester such as methyl, ethyl or butyl (meth)acrylate in the first step.
  • a diene such as cyclo- pentadiene or furane
  • a (meth)acrylate ester such as methyl, ethyl or butyl (meth)acrylate
  • the Diels- Alder product is transesterified in a single phase or an ester group is hydrolyzed to give a carboxylic acid group followed by preparation of an acid chloride from the acid.
  • the acid chloride is reacted with an alcohol, for instance with diethylene glycol or neopentyl glycol.
  • the double bonds present in the ester are oxidized for instance with m-chloroperbenzoic acid or peracetic acid to form epoxy groups.
  • Cycloaliphatic diesters may be prepared by reacting one of the above dienes with a di(meth)acrylate ester such as with ethyleneglycol dimethacrylate, di(ethyleneglycol)dimethacrylate or di(ethyleneglycol)diacrylate in the first step, followed by oxidation of the double bonds present in the cycloaliphatic ester to form epoxy groups in the second step.
  • a di(meth)acrylate ester such as with ethyleneglycol dimethacrylate, di(ethyleneglycol)dimethacrylate or di(ethyleneglycol)diacrylate
  • a catalyst used in the first step of a preferable embodiment preferably an alumin- ium chloride, lithium perchlorate, or diethyl aluminiun chloride, is suspended in a solvent, preferably to toluene, or dichloromethane.
  • the reaction may also be car- ried out thermally without any catalyst.
  • An acrylate ester, preferably methyl acry- late, followed by the diene dissolved to the reaction solvent, preferably freshly cracked cyclopentadiene is added to the suspension.
  • the reaction is allowed to proceed at a temperature ranging from -80 to +30 °C, preferably from 0 to 20 °C for at least 30 minutes, then the catalyst is washed with water from the reaction mixture, followed by separation of the organic layer and evaporation thereof to dryness.
  • the product may be further purified by distillation. It has surprisingly been found that for instance the methyl ester of 5-norbornene 2-carboxylic acid may be produced with high yields (typically at least 75 %) and in an highly pure form (purity over 99 %).
  • the free carboxylic acid is produced by hydrolyzing the ester preferably with a NaOH solution (5 - 15 %), typically at 40 - 70 °C at least for 30 minutes until the ester layer has completely disappeared.
  • the product is recovered by acidifying the basic solution with for instance hydrochloric acid solution, by separating the acid layer formed, washing and evaporating to dryness.
  • Acid chloride is prepared by further dissolving the free acid to an organic solvent such as dichloromethane and by adding oxalyl chloride and N,N-dimethylformamide to the solution. Also thionyl chloride may be used to produce the acid chloride.
  • the mixture is agitated at 0 - 30 °C at least for one hour until the yield of the acid chloride is no less than 85 %.
  • the product is recovered from the reaction mixture by evaporation of the solvent, and the excessive oxalyl chloride.
  • the amount of oxalyl chloride is preferably 3 - 7 times the amount of the carboxylic groups of the acid, the amount of N,N-dimethyl formamide being 0 - 1.0 times the amount of oxalyl chloride.
  • the mono- or diester is prepared by adding the acid chloride to a mixture of a mono- or dialcohol, e.g. diethyleneglycol, and pyridine.
  • a mono- or dialcohol e.g. diethyleneglycol
  • pyridine e.g. diethyleneglycol
  • the reaction is allowed to take place at 10 - 30 °C for at least two hours until the ester yield is no less than 90 %, normally at least 95 %.
  • the product is recovered by extracting the reaction mixture with dichloromethane, washing the organic phase, drying and evaporating to dryness.
  • Both pyridine and alcohol are preferably used in amounts of 1.0 molar equivalents relative to the acid chloride.
  • the double bonds present in the ester are oxidized to give epoxy groups.
  • This epoxydation is preferably carried out by reacting the ethylenically unsaturated ester with peracetic acid while dichloromethane serves as the solvent.
  • the reaction is suitably carried out at 10 - 35 °C for at least two hours until the epoxide ester yield is no less than 90 %, typically at least over 95 %.
  • the molar ratio of the peracid to the double bonds in the ester reactant is from 1.1 to 1.6 fold.
  • the product is recovered by washing the reaction mixture with water and a basic solution followed by separation of the organic layer and evaporation thereof to dryness.
  • diethyleneglycol di(5,6- epoxy-2-norbornane carboxylate) may be produced with a very high yield (yield more than 96 %) in an highly pure form (purity over 94 %).
  • Acids suitable for the production of the esters of the mvention generally include saturated or ethylenically unsaturated mono- or dicarboxylic acids having a straight or branched chain and from 2 to 20, preferably 4 - 18 carbon atoms.
  • Acids particularly suitable as starting materials of aliphatic epoxide esters used in coating compositions include fatty acids such as oleic acid, linolenic acid, and linolic acid, natural oils such as tall oil, linseed oil, and rapeseed oil, acrylic acid, methacrylic acid, adipic acid, fumaric acid, maleic acid, succinic acid, glutaric acid, 9-decenoic acid, 6-heptenoic acid, 2-, 3- and 4-pentenoic acids, crotonic acid, vinyl acetic acid, 2-hexenoic acid, and 2-ethyl-2-hexenoic acid.
  • Alcohols suitable for the invention that may be used to produce epoxide ethers and esters include the following monohydric alcohols, diols and triols. Alcohols suitable for the present purpose include saturated or ethylenically unsaturated monohydric alcohols, diols and triols having a straight or branched chain and from 2 to 20 carbon atoms.
  • Alcohols particularly suitable as starting materials of aliphatic epoxide esters used in coating compositions may be exemplified by such mono- hydric alcohols as crotyl alcohol, 1-butanol, 2-butanol, isobutanol, 1-pentanol, 2- methyl-1-pentanol, isopentanol, 1-hexanol, 2-ethylhexanol, 2-ethyl-2-hexen-l-ol, 1-heptanol, 1-octanol, such diols as 2-ethyl-l,3-hexanediol, ethylene glycol, di- ethylene glycol, neopentyl glycol, 2-butyl-2-ethyl- 1,3 -propane diol, methylpro- pane diol, 1,4-butane diol, 1,6-hexane diol, 1,2- and 1,3-propane diols
  • Alkyl halides suitable in the invention for producing ethers include 4-bromo-l- butene, and 5-bromo-l-pentene.
  • Suitable dienes for producing cycloaliphatic epoxide compounds of the invention include cyclopentadiene, furane, and 1,3-cyclohexadiene.
  • Dienophils preferable for the invention include methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, and butyl methacrylate.
  • aliphatic and cycloaliphatic epoxide derivatives and glycidyl ethers and glycidyl esters may be used for producing various compositions. They may for instance be added to aqueous or solvent-based dispersions containing binders, as well as additives and adjuvants known as such. It is particu- larly preferable to produce aqueous dispersions. Binders known for latex paints such as polyvinyl acetate, polyacrylates, and copolymers thereof may serve as binders.
  • polyvinyl acetates and polyacrylates consist of polymers of ethyleni- cally unsaturated monomeric units preferably produced using emulsion polymerization technique.
  • Said monomers are typically selected from a group consisting of vinyl acetate, vinyl alcohol, ethylene, propylene, butadiene, styrene, acryl nitrile, itaconic acid, maleic acid, fumaric acid, acrylic and methacrylic acids, and branched or linear C1-C9 esters, particularly C -C 8 esters thereof.
  • Typical useful esters of (meth)acrylic acid include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, butyl acrylate, butyl methacrylate.
  • the polymer may also comprise monomers having several reactive groups. Typical reactive groups present in the monomers include hydroxyl groups (e.g. hydroxy ethyl (meth)acrylate), amine gropus, car- bonyl groups (e.g.
  • diacetone acrylate diacetone acrylamide, acrolein, acetoace- toxy ethyl methacrylate), urea groups, and epoxide groups (e.g. glycidyl methacrylate).
  • monomers typical examples of which include acryl amide and derivatives thereof (e.g. N-methylol acrylamide and N-isobutoxy methyl acrylamide, and various compounds having more than one double bond, such as divinyl benzene.
  • Binders that may be dispersed in water, exemplified by various water-soluble polymers such as polyvinyl alcohol (PVA), starch, carboxy methyl cellulose (CMC), and hydroxy ethyl cellulose, may also be used.
  • PVA polyvinyl alcohol
  • CMC carboxy methyl cellulose
  • hydroxy ethyl cellulose may also be used.
  • alkyd resins may be used as binders. They normally include condensation products of a bivalent polyol and a fatty acid or a natural oil.
  • the epoxide compounds of the invention may be used in coating compositions including paint, varnish, joint mortar, filler mortar, mortar, and adhesive composi- tions, preferably in aqueous compositions, and particularly preferably in compositions based on latexes, for instance in paints containing a binder that forms a film after the coating has dried.
  • the amount of the polymer dispersion serving as a binder in the coating composition typically varies between 20 % and 80 %.
  • Suitable binders include e.g. polyacrylate latexes wherein styrene is polymerized with one or more acrylate or methacrylate monomer(s).
  • Such latexes are represented by carboxy functional styrene-acrylate latexes such as styrene-methylmethacrylate or styrene-butyl acrylate latexes.
  • preferable monomer combinations include styrene-butyl (meth)acrylate-(meth)acrylic acid, styrene-2-ethylhexyl (meth)acrylate-(meth)acrylic acid, methyl (meth)acrylate-butyl (meth)acrylate- (meth)acrylic acid, and methyl (meth)acrylate-butyl (meth)acrylate-hydroxy ethyl (meth)acrylate.
  • coalescent agents of the invention in combination with styrene-butyl acrylate-(meth)acrylic acid and a commercially available sty- rene-acrylate-latex (Dispersion A) is described in Example 5 below.
  • the polymer typically comprises from 20 to 80 %, preferably from 40 to 60 % of the dispersion.
  • the polymer dispersions typically contain one or more surface active agent(s), preserving agents, antifoam agents, and agents for pH control, for instance aqueous ammonia. Dispersing and thickening agents may be mentioned as other possible additives and adjuvants.
  • the amount of the epoxide compounds in the coating composition varies between 1 and 10 % by weight, preferably from 4 to 7 % by weight.
  • the epoxide compounds may act as efficient mould inhibitors in the coatings used particularly on inert surfaces such as metal, glass, or plastic surfaces, also on surfaces made of wood or materials derived from wood. In this manner, the use of traditional fungicides may be totally avoided or at least the amount thereof considerably reduced.
  • the pH value of the coating compositions is neutral, slightly basic or acidic, more preferably neutral or slightly acidic.
  • the pH value of the coating composition is more preferably lower than about 8.5, most preferably below 8.0.
  • the compounds of the invention may be used for producing both monocomponent and bi component coatings wherein the other component is added only prior to the use of the coating composition.
  • the present coalescent agents are compared to commercially available products.
  • the epoxide compounds of Examples 1 - 4 have a lowering effect on the film forming temperature.
  • the VOC indexes of all epoxide compounds produced are at least higher than 1500, usually higher than 2000, and accordingly, due to low volatilities, the use thereof is safer that that of traditional reactive coalescent agents, and moreover, they are not classified as NOC compounds.
  • VOC index RI 1000* (t a /tci4).
  • t a represents the retention time of the epoxide compound analyzed
  • t ⁇ 4 is the retention time of tetradecane used as the internal standard.
  • the 5-norbornene-2-carboxylic acid was prepared by mixing 164 mmol (25.0 g) of the methyl ester with 85 g of 10 % NaOH solution at 60 °C until the ester layer disappeared. Further, the solution was cooled, washed with diethyl ether and poured to 235 ml of 1 M hydrochloric acid at 60 - 70 °C while agitating. The acid layer formed was separated, dissolved in ethyl acetate, washed with water, dried with anhydrous sodium sulfate, filtered and concentrated to dryness in vacuum. The yield was 18.2 g (80 %). ! H and 13 C NMR spectra showed that the product was a relatively pure 5-norbornene-2-carboxylic acid.
  • the diester was prepared by adding 115 mmol (18.0 g) of the acid chloride from the previous step to a mixture of diethylene glycol (57.5 mmol, 6.10 g) and pyri- dine (115 mmol, 9.09 g) at room temperature. The mixture was agitated at room temperature for 4 hours, followed by the addition of 150 ml of dichloromethane and 100 ml of water to the mixture. The organic layer was further washed with water, sodium bicarbonate solution and hydrochloric acid solution, followed by drying with anhydrous sodium sulfate. The mixture was filtered and concentrated to dryness to give a yellow oil as the residue. The yield was 18.9 g (95 %). 1H and 13 C NMR spectra showed that the product mainly consisted of a diester.
  • Diethyleneglycol di(5,6-epoxy-2-norbornane carboxylate) was prepared by dissolving 54.5 mmol (18.9 g) of the diester from the above step to 260 ml of di- chloromethane. Further, 15.3 mmol (2.08 g) of sodium acetate trihydrate was dissolved in 39 % solution of peracetic acid in acetic acid (153 mmol, 29.8 g). The mixture was added drop wise to the diester solution in 30 minutes. The reaction mixture was agitated for 4 hours at room temperature. After the agitation, the re- action mixture was washed with water and sodium bicarbonate solution.
  • Example 2 The performance of the coalescent agent prepared in Example 2 in paint mixtures was further tested by preparing a mixture of a commercially available styrene- acrylate-latex (Dispersion A) with 6 % by weight of a reactive coalescent agent. A mixture was also prepared from a poly(styrene-co-n-butyl acrylate-co-methacrylic acid)latex by adding thereto a reactive coalescent agent in an equimolar amount, relative to carboxylic acid groups. A commercially available coalescent agent, butyl diglycol acetate, served as a control. Table 4 below shows the influence of the reactive coalescent agent prepared in Example 2 on the solvent resistance of two different dispersions (MEK abrasion test, ASTM D 4752) in comparison to a commercially available coalescent agent.
  • MEK abrasion test ASTM D 4752
  • Mould inhibition activities of some coalescent agents of the glycidyl type were measured according to ASTM D4300-98a using a glass fiber filter disc (Tables 5 & 6) and birch veneer (Table 7).
  • a coalescent agent was added in an amount of 6 % by weight to a commercially available styrene-acrylate latex (Dispersion A) (Tables 5 & 6), or to a commercially available polyvinyl acetate latex (Dispersion B) (Table 7), followed by determination of the mould inhibition activities of these mixtures made of the coalescent agent and the dispersion according to the method.
  • mould inhibitor containing from 7 to 10 % by weight of 3-iodo-2-propynylbutyl carbamate and from 3 to 5 % by weight of 2-(methylthio)- 4-(tert-butylamino)-6-(cyclopropylamino)-s-triazin was added in an amount of 1.5 % by weight.
  • mould inhibitor containing from 7 to 10 % by weight of 3-iodo-2-propynylbutyl carbamate and from 3 to 5 % by weight of 2- (methyl thio)- 4-(tert-butylamino)-6-(cyclopropylamino)-s-triazin was added in an amount of 1.5 % by weight.

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  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Epoxy Compounds (AREA)
  • Epoxy Resins (AREA)
  • Paints Or Removers (AREA)

Abstract

31 Tiivistelmä Keksinnön kohteena on yhden tai useamman epoksidin käyttöhomeenestoaineena, joka epoksidi on alifaattinen epoksidiesteri tai -eetteri tai glysidyyliesteri tai - eetteri, sekä menetelmä homeen muodostumisen ehkäisemiseksi.
PCT/FI2005/050103 2004-03-22 2005-03-22 Use of epoxides as fungicides WO2005089549A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP05731351A EP1727425A1 (en) 2004-03-22 2005-03-22 Use of epoxides as fungicides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI20040430 2004-03-22
FI20040430A FI116844B (fi) 2004-03-22 2004-03-22 Reaktiiviset kalvonmuodostajat

Publications (1)

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WO2005089549A1 true WO2005089549A1 (en) 2005-09-29

Family

ID=32039449

Family Applications (2)

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PCT/FI2005/050102 WO2005090501A1 (en) 2004-03-22 2005-03-22 Reactive coalescent agents
PCT/FI2005/050103 WO2005089549A1 (en) 2004-03-22 2005-03-22 Use of epoxides as fungicides

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Application Number Title Priority Date Filing Date
PCT/FI2005/050102 WO2005090501A1 (en) 2004-03-22 2005-03-22 Reactive coalescent agents

Country Status (3)

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EP (2) EP1727870A1 (fi)
FI (1) FI116844B (fi)
WO (2) WO2005090501A1 (fi)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2055708A1 (en) * 2006-08-15 2009-05-06 Showa Denko K.K. Novel epoxy compound and process for production thereof
US20140018568A1 (en) * 2011-03-25 2014-01-16 Korea Research Institute Of Chemical Technology Norbornene-ester-based derivative, method for preparing same, and uses thereof
EP2531496B1 (en) * 2010-02-02 2017-03-15 Hexion Research Belgium SA Manufacture of an epoxyethyl carboxylate or glycidyl carboxylate
CN115028804A (zh) * 2022-06-16 2022-09-09 深圳市恒纬祥科技有限公司 一种用于半导体灌封胶的脂环环氧树脂及其合成方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101609277B1 (ko) 2008-01-31 2016-04-05 로디아 오퍼레이션스 효율적인 응집제
FR2950051B1 (fr) 2009-09-11 2012-08-03 Centre Nat Rech Scient Nouveau procede de preparation de polyols et produits tels qu'obtenus
JP2015214497A (ja) * 2014-05-08 2015-12-03 国立大学法人山形大学 新規多官能グリシド酸エステル化合物及びその製法ならびにそれを用いたポリマー
CN108047168B (zh) * 2017-12-20 2021-02-26 东南大学 一种环氧油酸缩水甘油酯的合成方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2152003A (en) * 1935-10-29 1939-03-28 Shell Dev Insecticide and fumigant
EP0154806A2 (de) * 1984-02-15 1985-09-18 Bayer Ag Substituierte Oxirane
WO2000044836A1 (fi) * 1999-01-18 2000-08-03 Dynea Chemicals Oy Paint compositions

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB953761A (en) * 1960-09-15 1964-04-02 Dow Chemical Co Thermosettable coating formulations and coated articles
US4276211A (en) * 1980-03-10 1981-06-30 Troy Chemical Corporation Stabilization composition for coating composition
US4297258A (en) * 1980-04-28 1981-10-27 Ici Americas Inc. Non-yellowing paint formulations containing iodo substituted alkynyl urethanes as fungicides
CA1328175C (en) * 1988-05-16 1994-04-05 John Robert Mattox Epoxide stabilizers for biocidal compositions
US4959399A (en) * 1988-05-20 1990-09-25 W. R. Grace & Co.-Conn. Acidic adhesion promoters for PVC plastisols
US6201070B1 (en) * 1996-11-20 2001-03-13 Union Carbide Chemicals & Plastics Technology Corporation Method for enhancing the toughness of cycloaliphatic epoxide-based coatings
US6059991A (en) * 1997-12-12 2000-05-09 Troy Technology Corporation, Inc. Stabilized composition containing halopropynyl compounds
US6140370A (en) * 1998-09-21 2000-10-31 Troy Technology Corporation, Inc. Stabilized alkyd based compositions containing halopropynl compounds

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2152003A (en) * 1935-10-29 1939-03-28 Shell Dev Insecticide and fumigant
EP0154806A2 (de) * 1984-02-15 1985-09-18 Bayer Ag Substituierte Oxirane
WO2000044836A1 (fi) * 1999-01-18 2000-08-03 Dynea Chemicals Oy Paint compositions

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2055708A1 (en) * 2006-08-15 2009-05-06 Showa Denko K.K. Novel epoxy compound and process for production thereof
EP2055708A4 (en) * 2006-08-15 2011-01-26 Showa Denko Kk NEW EPOXY COMPOUND AND METHOD FOR THE PRODUCTION THEREOF
JP5153635B2 (ja) * 2006-08-15 2013-02-27 昭和電工株式会社 新規エポキシ化合物およびその製造方法
EP2531496B1 (en) * 2010-02-02 2017-03-15 Hexion Research Belgium SA Manufacture of an epoxyethyl carboxylate or glycidyl carboxylate
US20140018568A1 (en) * 2011-03-25 2014-01-16 Korea Research Institute Of Chemical Technology Norbornene-ester-based derivative, method for preparing same, and uses thereof
CN103547557A (zh) * 2011-03-25 2014-01-29 祥明大学校首尔产学协力团 降冰片烯-酯类衍生物、其制备方法及其用途
EP2690085A2 (en) * 2011-03-25 2014-01-29 Sangmyung University Seoul Industry-Academy Cooperation Foundation Norbornene-ester-based derivative, method for preparing same, and uses thereof
JP2014522376A (ja) * 2011-03-25 2014-09-04 サンミュン大学校ソウル産学協力団 ノルボルネンエステル系誘導体、その製造方法およびその用途
EP2690085A4 (en) * 2011-03-25 2014-09-24 Univ Sangmyung Seoul Industry Academy Cooperation Foundation NORBORNENE ESTER DERIVATIVE, PROCESS FOR PRODUCING THE SAME AND USES THEREOF
US9040737B2 (en) 2011-03-25 2015-05-26 Sangmyung University Seoul Industry-Academy Cooperation Foundation Norbornene-ester-based derivative, method for preparing same, and uses thereof
CN115028804A (zh) * 2022-06-16 2022-09-09 深圳市恒纬祥科技有限公司 一种用于半导体灌封胶的脂环环氧树脂及其合成方法

Also Published As

Publication number Publication date
FI116844B (fi) 2006-03-15
FI20040430A0 (fi) 2004-03-22
EP1727425A1 (en) 2006-12-06
EP1727870A1 (en) 2006-12-06
WO2005090501A1 (en) 2005-09-29
FI20040430A (fi) 2005-09-23

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